I still recommend taking the 685 bus (sometimes $5, sometimes free of cost) to Gila Bend to start trips west toward California - it is great for San Diego, Yuma, and Los Angeles. I no longer recommend trying to get to Tucson via Ajo, however. I would recommend leaving South of Chandler to get to Tucson!
Great spot to leave the valley heading south, I have started trips to Tucson from here. It is 5 miles south of the nearest bus stop, so requires a little walking or a ride, but worth it to catch the reservation traffic.
Plenty of shoulder if you walk a little past the light. Cars are going fast, but!, they can see you at a distance and the ones caught at the light have even more time to consider pulling over. I caught a ride all the way to Colorado from here.
I just want to comment that these spot reviews were for the gas station south of these coordinates, 35.2396, -111.6717 ☍
I hitched to the Grand Canyon there a dozen or so times with success. Wait times varied based on time of day, time of year, and number of people.
I have left from this spot SO many times. Best way to go North out of the valley. Take the lightrail all the way east to Gilbert Rd. Take the Gilbert Rd bus (doesn't run Sundays) all the way north. Walk about two more miles to where Gilbert road ends. Guaranteed rides, no cop harassment. Everyone is going at least to Fountain Hills, a good half the traffic is heading to Payson or beyond. I have started trips to Flagstaff, Payson, Chinle, Moab, Las Vegas, Santa Fe, and more from this spot. Worth it to take this highway over the I-17 any day. Wait times tend to be short.